MX2013000798A - (4-halogenalkyl-3-thiobenzoyl)cyclohexanediones and use thereof as herbicides. - Google Patents

Abstract

The invention relates to (4-halogenalkyl-3-thiobenzoyl)cyclohexanediones of general formula (I) and to the use thereof as herbicides. In said formula (I), X, Y, R¹, R², R³and R⁴ represent radicals such as hydrogen and organic radicals such as alkyl. A and Z represent oxygen or alkene.

Description

(4-HALOALQUIL-3-TIOBENZOIL) CICLOHEXANODIONAS AND ITS USE AS HERBICIDES FIELD OF THE INVENTION The invention relates to the technical field of herbicides, more particularly to that of herbicides for the selective control of broadleaf weeds and weeds in crops of useful plants.

BACKGROUND OF THE INVENTION It is known from various publications that certain benzoylcyclohexanediones have herbicidal properties. For example, EP 0 338 992 A1 and WO 2011/012247 A 1 each describe 2- (3-alkylthiobenzoyl) cyclohexanediones substituted by various radicals. US 2002/165096 A1 and DE 19961465 A1 disclose benzoylcyclohexanediones carrying a sulfur radical attached directly in the 3-position of the phenyl ring.

However, the herbicidal activity of the compounds known from these publications is often inadequate. It is therefore an object of the present invention to provide compounds having herbicidal activity whose herbicidal properties are better in comparison with the known compounds of the prior art.

DESCRIPTION OF THE INVENTION It has now been found that certain benzoylcyclohexanediones whose cyclohexanedione ring has a bridge and whose phenyl ring carries a thio group in position 3 and a haloalkyl group in position 4 are especially suitable as herbicides. The present invention first provides (4-haloalkyl-3-thiobenzoyl) cyclohexanediones with the formula (I) or its salts in which X is alkyl (Ci-C4), And it is haloalkyl (C-1-C4) or trifluoromethyl, A and Z are independently from each other oxygen, -S (0) m-, -N (R5) -, carbonyl or alkylene (C1-C4) which is interrupted by q units of the group consisting of oxygen, -S (0) m -, -N (R5) - and carbonyl, and which is substituted with radicals R6, R1 is (C1-C4) alkyl, R2 is hydroxyl, SR7, NR8R9, R3 and R4 are independently from each other hydrogen or (C1-C4) alkyl, R5 is hydrogen, alkyl (CrC4), alkoxy (C1-C4), alkylcarbonyl (C1-C4), alkoxycarbonyl (C1-C4), phenylcarbonyl or phenoxycarbonyl, the phenyl ring in the last two mentioned radicals which is substituted with up to p atoms of halogen and with up to p radicals of the group consisting of nitro, cyano, alkyl (C4), haloalkyl (C1-C4), alkoxy (dC), and haloalkoxy (C1-C4), R6 is halogen, (C1-C4) alkyl, haloalkyl (CrC4), alkoxy (CrC4), haloalkoxy (Cr C4) or alkoxy (Ci-C4) -alkyl (C1-C4), R7 is (C1-C4) alkyl or is phenyl which is substituted with p halogen atoms or with p radicals from the group consisting of nitro, cyano, (C1-C4) alkyl, haloalkyl (Cr C4), (C1-C4) alkoxy , and (C1-C4) haloalkoxy, R8 is hydrogen, (C1-C4) alkyl or (C1-C4) alkoxy, R9 is hydrogen or (C1-C4) alkyl, or R8 and R9, with the nitrogen atom to which they are attached, form a 5 or 6 membered saturated, partially saturated or fully unsaturated ring containing additional m heteroatoms from the group consisting of oxygen, sulfur, and nitrogen, and which is substituted with up to s halogen atoms and with up to p radicals from the group consisting of cyano, (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, (C 1 -C 4) alkoxy, and (C 1 -C 4) haloalkoxy, m and n are independently of each other 0, 1 or 2, p is 0, 1, 2, 3, 4 or 5, q is 0 or 1, s is O, 1, 2, 3, 4, 5, 6, 7 or 8.

When R2 is hydroxyl, the compounds of the invention of formula (I) may exist in the form of different tautomeric structures, depending on external conditions, such as the solvent and pH, in the following manner: Depending on the nature of the substituents, the compounds with the Formula (I) contain an acidic proton that can be removed by reaction with a base. Examples of suitable bases include hydrides, hydroxides, and carbonates of lithium, sodium, potassium, magnesium, and calcium, and also ammonia and organic amines such as triethylamine and pyridine. In addition, salts can be formed by reaction with organic acids, such as formic acid or acetic acid, or with inorganic acids, such as phosphoric acid, hydrochloric acid or sulfuric acid. The present invention also provides said salts.

In formula (I) and all subsequent formulas, alkyl radicals with more than two carbon atoms can be straight or branched chain. Alkyl radicals are, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, tere- or 2-butyl, pentyl, hexyl, such as n-hexyl, iso-hexyl and 1, 3- dimethylbutyl. Halogen is fluorine, chlorine, bromine or iodine.

When a group is multiply substituted with radicals, this means that the group in question is substituted with one or more equal or different members selected from the specified radicals.

Depending on the nature and the binding of the substituents, the compounds of the formula (I) may be present in the form of steroisomers. When, for example, one or more sulfoxides or substituted carbon atoms are present asymmetrically, then enantiomers and. diastereomers The steroisomers can be obtained from the mixtures resulting from the preparation process by customary separation methods, such as, for example, chromatographic separation processes. It is also possible to selectively prepare steroisomers by the application of stereoselective reactions using starting materials and / or optically active auxiliaries. The invention also relates to all the steroisomers and their mixtures which are included in the formula (I) but which are not defined specifically.

Of particular interest are compounds with the formula (I) in which X is (C1-C4) alkyl, Y is haloalkyl (C1-C4) or trifluoromethyl, A and Z are independently oxygen or alkylene (C1-C4), R1 is alkyl (C4), R2 is hydroxyl, and R3 and R4 are independently hydrogen or (C1-C4) alkyl.

Preference is given to the compounds with the formula (I) in which X is alkyl (C C4), And it is trichloromethyl, difluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, pentafluoroethyl or heptafluoroisopropyl, A and Z are each alkylene (Ci-C4), R1 is (C1-C4) alkyl, R2 is hydroxyl, and R3 and R4 are independently hydrogen or (C1-C4) alkyl.

Particular preference is given to the compounds with the formula (I) wherein X is methyl, And it is chlorodifluoromethyl, difluoromethyl or pentafluoroethyl, A and Z are each independently CH2 or CH2CH2, R1 is methyl, R2 is hydroxyl, R3 and R4 are each hydrogen, and n is 1 or 2.

Particular preference is given to the compounds with the formula (I) in which X is methyl, And it's pentafluoroethyl, A and Z are each independently CH2 or CH2CH2, R1 is methyl, R2 is hydroxyl, R3 and R4 are hydrogen, and n is 1 or 2.

In all the formulas provided below, the substituents and symbols have the same meanings as described for formula (I), unless otherwise defined.

The compounds of the invention in which R2 is hydroxyl can be prepared, for example, by the process indicated in Scheme 1 and known, for example, from WO 03/084912, by a reaction catalyzed by a base of a derivative of the benzoic acid (III), in which L is alkoxy or halogen, with a cyclohexanedione (IV) and subsequent rearrangement. The intermediate compound (V) can also be prepared by direct reaction of a benzoic acid (II) with a cyclohexanedione (IV) with the addition of a condensation activating agent such as N- (3-dimethylaminopropyl) -N hydrochloride. '-ethylcarbodiimide, for example.

Scheme 1 (V) (I), where R2 = OH The compounds of the invention in which R2 has a different definition of hydroxyl are usefully prepared according to Scheme 2 from the compounds obtainable according to Scheme 1. The procedures of this type are basically familiar to the skilled person. and are described in WO 03/084912, for example.

Scheme 2 (I), where R2 is not equal to OH The cyclohexanediones with the formula (IV) are commercially available or can be prepared according to the method known to the skilled person and described in EP 0 338 992 and WO 2008/071405, for example. The preparation of benzoic acids with the formula (II) is known, for example, from WO 2008125214.

The benzoic acids (II) can be obtained by a series of synthetic steps per se known by the skilled person.

For example, the synthesis of benzoic acids carrying a trifluoromethyl group as a haloalkyl group in position 4 is known from WO 2008125214. Depending on the nature of the haloalkyl group, the processes described in said documents can be applied to the synthesis of benzoic acids (II).

Another possibility is the introduction of haloalkyl groups. For example, the introduction of a pentafluoroethyl group in position 4 of a benzonitrile is described in WO 2006/43064 and US 2007/185058. The benzonitrile can be subsequently converted to the corresponding benzoic acid (US 2007/185058). It is also known to replace the iodo aromatic compound with a haloalkyl group, a reaction that takes place through the corresponding copper haloalkyl compound (A. A. Kolomeitsev et al., J. Org. Chem. 2008, 73 (7), 2607.).

Alternatively, haloalkyl groups can be generated from other functional groups. A difluoromethyl group is accessible, for example, from the corresponding formyl group. A transformation of this type is described for 4-formylbenzonitrile by CP. Andrieux et al. (Journal of the American Chemical Society 1997 (119), 40, 9527). The corresponding benzoic acid can then be generated from the product under basic conditions, for example (F. Mathey et al., Tetrahedron 1975 (31), 391.).

Other possibilities for obtaining by synthesis benzoic acids that can be applied to the synthesis of benzoic acids (II) are known from WO 03/014071.

The sulfur atom in position 3 of the benzoyl group does not necessarily have to be oxidized in the benzoic acid stage in order to generate compounds with n = 1 or 2; for example, oxidation of this type may also be useful in the enol ester or benzoylcyclohexanedione step.

The benzoic acids with the formula (II) are new and are also supplied by the invention.

The collections of compounds with the formula (I) and / or their salts that can be synthesized by the aforementioned reactions can also be prepared in a parallel manner, this being possible to take place manually, partially automated or completely automated. In this connection, for example, it is possible to automate the reaction process, the final treatment or the purification of the products and / or intermediates. In general, this is understood to mean a process as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (Günther Jung editor), Verlag Wiley 1999, pages 1 to 34.

For the parallel reaction process and the final treatment, it is possible to use a series of commercially available instruments, for example, Calypso reaction blocks from Barnstead International, Dubuque, Iowa 52004-0797, USA; or reaction stations of Radleys, Shirehill, Saffron Walden, Essex, CB11 3AZ, England; or MultiPROBE automated workstations from Perkin Elmer, Waltham, Massachusetts 02451, USA. For the parallel purification of the compounds of the formula (I) and their salts or of the intermediates produced during the preparation, chromatographic apparatuses are available, for example, at ISCO, Inc., 4700 Superior Street, Lincoln , NE 68504, USA The listed devices give rise to a modular process in which the individual stages of the process are automated, but in which manual operations must be carried out between the stages of the process. This can be avoided by using partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be purchased, for example, from Caliper, Hopkinton, MA 01748, USA.

The implementation of one or several stages of synthesis can be supported by the use of reagents subject to polymer / sequestering resins. The specialized literature describes a series of experimental protocols, for example in ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).

Apart from the processes described in the present specification, the preparation of the compounds of the formula (I) and their salts can take place completely or partially by processes with solid phase supports. For this purpose, the individual intermediates or all intermediates in the synthesis or in a synthesis adapted to the corresponding process are linked to a synthesis resin. The synthesis procedures with solid phase supports have been sufficiently described in the specialized literature, for example, Barry A. Bunin in "The Combinatorial Index", Verlag Academic Press, 1998 and Combinatorial Chemistry - Synthesis, Analysis, Screening (editor Günther Jung ), Verlag Wiley, 1999. The use of synthesis procedures with solid phase supports allows a series of protocols known in the literature, which can again be carried out manually or in an automated way. The reactions can be carried out, for example, by means of IRORI technology in microreactors of Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.

The individual steps or the various stages of synthesis of a process in both solid phase and liquid phase can be supported in the use of microwave technology. The specialized literature describes a series of experimental protocols, for example, in Microwaves in Organic and Medicinal Chemistry (editors C. O. Kappe and A. Stadler), Verlag Wiley, 2005.

The preparation according to the process described in the present specification produces compounds with the formula (I) and their salts in the form of collections of substances that are called libraries. The present invention also provides libraries comprising at least two compounds of formula (I) and their salts.

The compounds of the formula (I) according to the invention (and / or their salts), also collectively referred to hereafter as "compounds according to the invention", exhibit excellent herbicidal efficacy against a broad spectrum of important monocotyledonous or dicotyledonous annual weeds. The active compounds act efficiently even on perennial weeds that produce buds from rhizomes, roots root caps and other perennial organs and which are difficult to control.

Therefore, the present invention also relates to a method for the control of unwanted plants or to regulate the growth of plants, preferably in plant crops, wherein one or more compound (s) according to the invention is applied to the plants (for example, harmful plants such as monocotyledonous or dicotyledonous weeds or unwanted crop plants), to seeds (for example, grains, seeds or vegetative propagules such as tubers or shoots with buds) or to the area in which plants grow (for example, the cultivation area). In this context, the compounds according to the invention can be applied, for example, before sowing (if necessary also by incorporation into the soil), before emergence or after emergence. Specific examples of some representatives of monocotyledonous and dicotyledonous weeds can be mentioned that can be controlled with the compounds according to the invention, without the enumeration being restricted to certain species.

Detrimental monocotyledonous plants of the genus: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Oats, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Broadleaved dicotyledonous weeds of the genus: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum , Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex , Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

If the compounds according to the invention are applied on the surface of the soil before germination, the emergence of the weed seedlings or the growth of the weeds until they have reached the cotyledon phase is completely avoided, but then the it stops growing, and eventually, after three to four weeks have passed, they die completely.

If the active compounds are applied after emergence of the green parts of the plants, the growth stops after the treatment, and the harmful plants remain in the growth phase in which they were at the time of their application, or die completely after a certain time, so that competition from weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.

Despite the fact that the compounds according to the invention have an excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as, for example, dicotyledonous crops of the genus Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus. , Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous cultures of the genus Allium, Ananas, Asparagus, Oats, Hordeum, Oryza, Panicum, Saccharum, Sécale, Sorghum, Triticale , Triticum, Zea, in particular Zea and Triticum, are only unimportantly damaged, or not at all, depending on the structure of the respective compounds according to the invention and their rate of use. This is the reason why the present compounds are well suited for the selective control of growth of unwanted plants in plant crops such as agriculturally useful or ornamental plants.

In addition, the compounds according to the invention (depending on their respective structures and their applied application rates) exhibit excellent growth regulating properties in crop plants. They take part in the metabolism of the plant in a regulatory manner and can therefore be used to influence, in a targeted manner, the constituents of the plant and to facilitate collection, such as, for example, activating desiccation and growth retardation. In addition, they are also suitable for controlling and inhibiting in general the unwanted vegetative growth without destroying the plant in the process. The inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops since by the present invention, for example, colonization can be reduced or completely avoided.

By virtue of their herbicidal and plant growth regulating properties, the active compounds can also be used to control harmful plants in genetically modified plant cultures known or yet to be developed. In general, transgenic plants are distinguished by particularly advantageous properties, for example, by resistance to certain pesticides, mainly certain herbicides, resistance to plant diseases or to organisms causing plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other specific characteristics refer, for example, to the material collected in terms of quantity, quality, storage capacity, composition and specific constituents. Thus, transgenic plants are known whose starch content has increased, or the quality of whose starch has been altered, or those in which the collected material has a different fatty acid composition. Particular additional features may consist of tolerance or resistance to abiotic stressors, for example, heat, cold, drought, salinity, and ultraviolet radiation.

Preferred is the use of the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants, for example, of cereals such as wheat, barley, rye, oats, millet, rice, yucca and corn or other beet crops ^ sugar, cotton, soy, rapeseed, potato, tomato, peas and other vegetables.

It is possible to use preferably the compounds of the formula (I) as herbicides in crops of useful plants which are resistant, or which have become resistant by recombinant means, to the phytotoxic effects of the herbicides.

Commercial methods for generating new plants having modified properties compared to plants obtained to date consist of, for example, conventional culture methods and the generation of mutants. Alternatively, new plants with altered properties can be generated with the aid of recombinant methods (see, for example, EP 0221044, EP 0131624). For example, on several occasions the following has been described: The modification, by recombinant technology, of crop plants with the aim of modifying the starch synthesized in the plants (for example, WO 92/011376 A, WO 92/014827 A, WO 91/019806 A), Transgenic crop plants that are resistant to certain glufosinate-type herbicides (cf., for example, EP-A-0242236, EP-A-0242246) or glyphosate type (WO 92/000377 A) or of the sulfonylurea type (cf. EP-A-0257993, US 5,013,659), or to combinations or mixtures of these herbicides that are resistant as a result of 'gene stacking', such as transgenic crop plants, e.g., corn or soybeans, under the trade name or the designation Optimum ™ GAT ™ (glyphosate tolerant to ALS).

Transgenic crop plants, for example cotton, with the ability to produce toxins of Bacillus thuringiensis (Bt toxins), which render the plants resistant to certain pests (EP-A-0142924, EP-A-0193259), Transgenic crop plants with a modified fatty acid composition (WO 91/013972 A), Genetically modified crop plants with new constituents or secondary metabolites, for example new phytoalexins, which generate a greater resistance to diseases (EPA documents 0309862, EPA0464461), Genetically modified plants with a reduced photorespiration that produce higher yields and a greater tolerance to stress ( EPA document 0305398), Transgenic crop plants that produce pharmaceutically or diagnostically important proteins ("molecular biopharmaceutics"), Transgenic plants that are distinguished by higher yields or better quality, Transgenic crop plants that are distinguished by a combination, for example, of the aforementioned new properties ("stacking" gene ").

In principle, a large number of molecular biology techniques are known through which new transgenic plants with modified properties can be generated; see, for example, I. Potrikus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, "Trends in Plant Science" 1 (1996) 423-431.

To carry out these recombinant manipulations, nucleic acid molecules allowing mutagenesis or sequence variations can be introduced into plasmids by recombination of DNA sequences. For example, substitutions of bases can be carried out, partial sequences can be eliminated, or natural or synthetic sequences can be added with the aid of customary methods. To join DNA fragments together, it is possible to add adapters or linkers to the fragments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene und Klone", VCH Weinheim 2nd ed., 1996.

For example, the generation of plant cells with a gene product of reduced activity can be achieved by expressing at least one of the corresponding RNAs in the opposite direction, RNA in direct sense to achieve a cosuppressive effect or expressing at least one ribozyme conveniently constructed that cleaves specifically transcripts of the aforementioned gene product.

For this, it is possible to use DNA molecules that cover the entire coding sequence of a gene product, including all the flanking sequences that may be present, and also DNA molecules that only encompass parts of the coding sequence, making it necessary for these parts to be long enough to have an effect in the opposite direction on the cells. It is also possible to use DNA sequences which have a high degree of homology with the coding sequences of a gene product, but which are not completely identical to them.

When nucleic acid molecules are expressed in plants, the synthesized protein can be located in any desired compartment of the plant cell. However, to achieve location in a particular compartment, for example, it is possible to bind the coding region of DNA sequences that guarantee localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Nati. Acad. Sci. 85 (1988), 846-850; Sonnewaid et al., Plant J. 1 (1991), 95-106). Nucleic acid molecules can also be expressed in the organelles of plant cells.

The transgenic plant cells can be regenerated by known techniques to give rise to whole plants. In principle, the transgenic plants can be plants of any desired plant species, that is, not only monocotyledonous plants, but also dicotyledonous plants.

Thus, transgenic plants whose properties are altered by overexpression, suppression or inhibition of genes or homologous gene sequences (= natural) or the expression of genes or heterologous gene sequences (= exogenous) can be obtained.

The use of the compounds (I) according to the invention is preferred in transgenic crops that are resistant to growth regulators such as, for example, 2,4 D dicamba, or to herbicides that inhibit enzymes essential for plants, for example, acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenyl-pyruvate dioxygenases (HPPD), or to herbicides of the group of sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and analogous active compounds, or to any combination of these active compounds.

With particular preference the compounds according to the invention can be used in transgenic crop plants that are resistant to the combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. With very particular preference, the compounds according to the invention can be used in transgenic cultivation plants such as, for example, corn or soybeans under the trade name or the designation Optimum ™ GAT ™ (glyphosate tolerant to ALS).

When the active compounds according to the invention are used in transgenic crops, effects are often observed - in addition to the effects on harmful plants that can be observed in other crops - which are specific for their application in the transgenic crops in question, for example, a modified or specifically expanded spectrum of weeds that can be controlled, modified use rates that can be used for their application, preferably a good combination capacity with the herbicides to which the transgenic crop is resistant, and an effect on the growth and the performance of transgenic crop plants.

Therefore, the invention also relates to the use of the compounds of the formula (I) according to the invention as herbicides for the control of harmful plants in transgenic crop plants.

The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, powdered products or granules in customary formulations. Therefore, the invention also provides herbicidal compositions and which regulate the growth of the plants comprising the compounds according to the invention.

The compounds according to the invention can be formulated in various ways according to which biological and / or physicochemical parameters are mandatory. Possible formulations include, for example: wettable powders (WP), water soluble powders (SP), water soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil in water and water in oil emulsions, solutions sprays, suspension concentrates (SC), oil-based or water-based dispersions, oil miscible solutions, capsule suspensions (CS), powder products (DP), disinfectants, granules for dispersion and application on the ground granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual types of formulation are in principle known and described, for example, in: Winnacker-Küchier, "Chemische Technologie" [Chemical technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Driing" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation aids, such as inert materials, surfactants, solvents and additional additives, are also known and described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers," 2nd Ed., Darland Books, Caldwell NJ; H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergent and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzfláchenaktive Áctilenoxidaddukte" [Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchier, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.

Based on these formulations it is also possible to produce combinations with other compounds with pesticidal activity, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with protective agents, fertilizers and / or growth regulators, for example in the form of a formulation final or in the form of tank mix. Suitable protective agents are, for example, mefenpyr-diethyl, ciprosulfamide, ethyl isoxadifen, cloquintocet-mexyl and dichlormid.

Wettable powders are preparations that can be uniformly dispersed in water and, in addition to the active compound, and apart from a diluent or inert substance, also comprise ionic and / or nonionic surfactants (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, polyglycol ether sulphates of fatty alcohols, alkane sulphonates, alkylbenzene sulphonates, sodium lignosulfonates, 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalene sulfonate or other sodium oleoylmethyl taurinate. To prepare the wettable powders, the active compounds as herbicides are ground very finely, for example, in conventional apparatuses such as hammer mills, blow mills and air jet mills, and are mixed simultaneously or subsequently with the formulation auxiliaries.

The emulsified concentrates are prepared by dissolving the active compound in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or other aromatics or hydrocarbons with a relatively high boiling point or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). The emulsifiers used can be, for example: calcium alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as polyglycol esters of fatty acids, alkylaryl polyglycol ethers, polyglycol ethers of fatty alcohols, condensation products of propylene oxide-oxide of ethylene, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example esters of polyoxyethylene sorbitan fatty acids.

The powders are obtained by grinding the active compound with finely distributed solids, for example, talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

The suspension concentrates can be water-based or oil-based. They can be prepared, for example, by wet milling by means of commercial grain mills and the optional addition of surfactants such as those already mentioned above for the other types of formulation.

Emulsions, for example oil-in-water (EW) emulsions, can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants such as those already mentioned above for the other types of formulation.

The granulates can be prepared by spraying the active compound on a granular inert material capable of producing adsorption or with the application of concentrates of active compound on the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, example polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the usual way for the preparation of fertilizer granules - if desired as a mixture with fertilizers.

The water-dispersible granules are prepared in a general manner by customary methods such as spray-drying, granulation of the fluidized bed, casserole granulation, mixing with high-speed mixers and extrusion without inert solid material.

For the preparation of the granules in a pan, in a fluidized bed, in an extruder and by spray, see, for example, the procedures in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, p. 8-57.

For more details regarding the formulation of compositions for crop protection, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook," 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

Agrochemical formulations in general contain between 0.1 and 99% by weight, in particular between 0.1 and 95% by weight, of compounds according to the invention. In wettable powders, the concentration of active compound is, for example, between 10 and 90% by weight approximately, the rest up to 100% by weight consists of usual formulation components. In the case of emulsifiable concentrates, the concentration of active compound may be between about 1 and 90%, preferably between 5 and 80% by weight. Formulations in the form of powders comprise between 1 and 30% by weight of active compound, usually preferably between 5 and 20% by weight of active compound; the sprayable solutions contain between 0.05 and 80% by weight, preferably between 2 and 50% by weight of active compound. In the case of water-dispersible granules, the content of active compound depends partly on whether the active compound is present in liquid or solid form and on which granulation auxiliaries, fillers, etc., are used. In the water-dispersible granules, the content of the active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the above-mentioned active compound formulations optionally comprise the respective adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and colorants, defoamers, evaporation inhibitors and pH modifying agents. and the usual viscosity.

Based on these formulations, it is also possible to produce combinations with other compounds with pesticidal activity, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with protectants, fertilizers and / or growth regulators, for example, in the form of a formulation.; final or in the form of tank mix.

The active compounds which can be used in combination with the compounds according to the invention in mixed formulations or in tank mixtures are, for example, known active compounds based on the inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase. , enolpyruvil-shikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase,: | phytoene desaturase, photosystem I, photosystem II, proto-porphyrinogen oxidase, as described in, for example, Weed Research 26 (1986) 441- 445 or "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. Of Chemistry, 2006 and the bibliography cited therein. Herbicides or growth regulators of the known plants which can be combined with the compounds according to the invention are, for example, the following active compounds (the compounds are designated by the common name according to the International Organization for Standardization (ISO) or by the International Organization for Standardization (ISO)). chemical name, or by the code number) and always include all forms of use such as acids, salts, esters and isomers such as stereoisomers and optical isomers. In the present document, mention is made, by way of example, of one and in some cases a plurality of forms of use: acetochlor, acibenzolar, acibenzoJar-S methyl, acifluorfen, acifluorfen sodium, aclonifen, alachlor, alidochlor, alloxydim, alloxydim sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminociclopiraclor, aminopiralid, amitrol, ammonium sulfamate, ancimidol, anilofos, asulam, atrazine, azaphenidine, azimsulfuron, aziprotrin, beflubutamide, benazoline, ethyl benazoline, bencarbazone, benfluralin, benfurester, bensulide, bensulfuron, methyl bensulfuron, bentazone, benzephenone, benzobicyclone, benzofenap, benzofluor, benzoylprop, bicyclopirone, bifenox, bilanafos, bilanafos sodium , bispyribac, bispyribac sodium, bromacil, bromobutide, bromophenoxy, bromoxynil, bromuron, buminaphos, bufochlor, butachlor, butafenacil, butamifos, butenaclor, butralin, butroxydim, butylate, cafenstrol, carbetamide, carfentrazone, ethyl carfentrazone, clometoxifen, chloramben, clorazifop, clorazifop-butyl, chlorbromuron, chlorbufam, chlorfenac, chlorfenac sodium, chlorfenprop, chlorof lurenol, methyl chlorflurenol, chloridazon, chlorimuron, ethyl chlorimuron, chlormequat chloride, chlorenthrophen, chlorophthalim, chlorothaluron, chlorotoluron, chlorsulfuron, cinidon, ethyl cinnamide, cinmethilin, cinosulfuron, clethodim, clodinafop, propargyl clodinafop, clofencet, clomazone, clomeprop, cloprop, clopiralula, cloransulam, methyl cloransulam, cumiluron, cyanamide, cyanazine, cyclanilide, cycloate, cyclo-sulfamuron, cycloxydim, cyclonon, cyhalofop, cyhalofopbutyl, cyperquat, cipracin, ciprazole, 2,4-D, 2,4- DB, daimuron / dimron, dalapon, daminozide, dazomet, n-decanol, desmedifam, desmethrin, detosyl pyrazolate (DTP), dialate, dicamba, diclobenil, dichlorprop, dichlorprop-P, diclofop, methyl diclofop, diclofop-P methyl, diclosulam, dietyl, diethyl ethyl, difenoxuron, difenzoquat, diflufenican, diflufenzopir, diflufenzopir sodium, dimefuron, dikegulac sodium, dimefuron, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-P, di metipin, dimetrasulfuron, dinitramine, dinoseb, dinoterb, difenamid, dipropetrin, diquat, diquat dibromide, dithiopyr, diuron, DNOC, ethyl eglinacin, endothelium, EPTC, esprocarb, ethalfluralin, etametsulfuron, methyl ethemethuron, ethephon, etidimuron, etiozin, etofumesate, ethoxyfen, ethoxyphene of ethyl, ethoxysulfuron, ethobenzanid, F-5331, i.e., N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4, 5-dihydro-5-oxo-1 H-tetrazol-1-yl] -phenyl] -ethanesulfonamide, F-7967, that is, 3- [7-chloro-5-fluoro-2- (trifluoromethyl) -1H- benzimidazol-4-yl] -1-methyl-6- (trifluoromethyl) pyrimidin-2,4 (1 H, 3 H) -dione, fenoprop, fenoxaprop, fenoxaprop-P, ethyl fenoxaprop, ethyl phenoxaprop-P, phenoxazulfone, fentrazamide, fenuron, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone sodium, flucetosulfuron, flucloralin, flufenacet (thiafluamide), flufenpir, ethyl flufenpyr, flumetralin, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxacin, flumipropin, fluometuron, fluorodifen, fluoroglycophene, ethyl fluoroglycophene, flupoxam, flupropacil, flupropanate, flupirsulfuron, flupyrsulfuron-methyl sodium, flurenol, flurenol -butyl, fluridone, flurocloridone, fluroxypir, fluroxypyr-meptil, flurprimidol, flurtamone, flutiacet, methyl flutiacet, flutiamide, fomesafen, foramsulfuron, forchlorfenuron, fosamin, furiloxifen, gibberellic acid, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P sodium, glyphosate, glyphosate-isopropylammonium, H-9201, that is, 0- (2, 4-dimethyl-6-nitrophenyl) -0-ethyl-1-propylphosphoramidothioate, halosafen, halosulfuron, methyl halosulfuron, haloxifop, haloxifop-P, haloxifop-ethoxyethyl, haloxifop-P-ethoxyethyl, haloxifop of methyl, haloxifop-P of methyl, hexacinone, HW-02, ie 1- (dimethoxyphosphoryl) -ethyl (2,4-dichlorophenoxy) acetate, imazametabenz, methyl imazametabenz, mazamox, imazamox-ammonium, imazapic, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin- ammonium, imazetapir, mazetapyr-ammonium, imazosulfuron, inabenfide, indanofan, indaziflam, indoleacetic acid (IAA), 4-indol-3-ylbutyric acid (IBA), iodosulfuron, iodosulfuron-methyl sodium, ioxinil, ipfencarbazone, isocarbamid, isopropalin, isoproturon, isouron, isoxaben, isoxaclortol, isoxaflutole, isoxapirifop, KUH-043, that is, 3- ( { [5- (d) fluoromethyl) -1-methyl-3- (trifluoromethyl) -1H-pyrrazol-4-yl] methyl.} sulfonyl) -5,5-dimethyl-4,5-dihydro-1,2-oxazole, karbutylate, ketospiradox, lactofen, lenacil, linuron, maleic hydrazide, MCPA, MCPB, MCPB methyl, ethyl and sodium, mecoprop, mecoprop sodium, mecoprop-butotyl, mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2 -ethylhexyl, mecoprop-P potassium, mefenacet, mefluidide, mepiquat chloride, mesosulfuron, methyl mesosulfuron, mesotrione, metabenzthiazuron, metam, metamifop, metamither, metazachlor, metazasulfuron, metazole, methiopirsulfuron, methiozolin, methoxyphenone, metildimron, 1-methylcyclopropene , methylisothiocyanate, methobenzuron, methobromuron, metolachlor, S-metolachlor, metosulam, methoxuron, metribuzin, metsulfuron, methylsulfuron it, molinate, monalide, monocarbamide, monocarbamide dihydrogenosulfate, monolinuron, monosulfuron, monosulfuron-ester, monuron, MT 128, that is, 6-chloro-N - [(2E) -3-chloroprop-2-en-1-yl ] -5-methyl-N-phenylpyridazin-3-amine, MT-5950, ie N- [3-chloro-4- (1-methylethyl) -phenyl] -2-methylpentanamide, NGGC-011, naproanilide, napropamide, Naptalam, NC-310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxy pyrazole, neburon, nicosulfuron, nipiraclofen, nitralin, nitrofen, sodium nitrophenolate (mixture of isomers), nitrofluorfen, nonanoic acid, norflurazon , orbencarb, orthosulfamuron, orizalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomephone, oxyfluorfen, paclobutrazol, paraquat, paraquat-dichlorid, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxamid, fenisopham, fenmedipham, phenmedipham of ethyl, picloram, picolinafeno, pinoxaden, piperofos, pirífenop, pirifenop-butyl, pretilaclor, primisulfuron, pri methyl misulfuron, probenazole, profluazole, procyanidin, prodiamine, prifluralin, profoxydim, prohexadione, prohexadione-calcium, prohidrojasmone, promised, prometrin, propane, propanil, propaquizafop, propane, propham, propisoclor, propoxycarbazone, propoxycarbazone sodium, propirisulfuron, propizamide, prosulfalin, prosulfocarb, prosulfuron, prinachlor, pyraclonil, pyraflufen, ethyl pyraflufen, pyrasulfotol, pyrazolinate (pyrazolate), pyrazole sulfur, Ethyl pyrazolamide, pyrazoxifen, pybibambenz, piribambenz-isopropyl, piribambenz-propyl, piribenzoxim, pyributicarb, pyridafol, pyridate, piriftalid, piriminobac, pyriminobac methyl, pirimisulfan, piritiobac, piritiobac sodium, piroxasulfone, piroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop , quizalofop of ethyl, quizalofop-P, quizalofop-P of ethyl, quizalofop-P-tefurilo, rimsulfurón, saflufenacil, secbumeton, sethoxydim, siduron, simazine, symmetry, SN-106279, that is (2R) -2 ( { 7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthyl] oxy) propanoate methyl, sulcotrione, sulfalate (CDEC), sulfentrazone, sulfometuron, methyl sulfometuron, sulphites ato (glyphosate-trimesium), sulfosulfuron, SYN-523, SYP-249, i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl-5- [2-chloro-4- ( trifluoromethyl) phenoxy] -2-nitrobenzoate, SYP-300, that is, 1 - [7-fluoro-3-oxo-4- (prop-2-yn-1-yl) -3,4-dihydro-2H-1 , 4-benzoxacin-6-yl] -3-propyl-2-t-oxoimidazolidin-4,5-dione, tebutam, tebutiuron, tecnazeno, tefuriltrione, tembotrione, tepraloxidim, terbacil, terbucarb, terbuclor, terbumeton, terbutilacin, terbutrin, Tenilchlor, thiafluamide, thiazafluron, thiazopyr, thidiazimine, thidiazuron, thiencarbazone, methyl thiencarbazone, thifensulfuron, methyl thifensulfuron, thiobencarb, thiocarbazyl, topramezone, tralcoxydim, trialate, triasulfuron, triaziflam, triazophenamide, tribenuron, methyl tribenuron, trichloroacetic acid (TCA) ), triclopyr, tridifone, trietacine, trifloxysulfuron, trifloxysulfuron sodium, trifluralin, triflusulfuron, methyl triflusulfuron, trimeturon, trinexapac, ethyl trinexapac, tritosulfuron, tsitodef, uniconazole, uniconazole P, vernolate, ZJ-0862 ie 3,4-dichloro-N-. { 2 - [(4,6-dimethoxypyrimidin-2-yl) oxy] benzyl} aniline, and also the following compounds: For use, formulations present in commercial form are diluted, if appropriate, in a customary manner, for example, in the case of wettable powders, emulsified concentrates, dispersions and granules dispersible in water, with water. Formulations in the form of powders, granules for use in soils or granules for spreading and sprayable solutions are normally not further diluted with other inert substances before use.

The rate of necessary use of the compounds of the formula (I) varies according to external conditions such as, among others, temperature, humidity and the type of herbicide used. It may vary within wide limits, for example, between 0.001 and 1.0 kg / ha or higher of active substance; however, it is preferably between 0.005 and 750 g / ha.

The following examples illustrate the invention.

A. Chemical examples Preparation of 3 - (- 2-methyl-3-methylsulfinyl-4-pentafluoroethyl) benzoyl) bicyclo [3.2.1] octane-2,4-dione (example of table No. 1-153) Stage 1: Synthesis of 3-fluoro-4- (pentafluoroethyl) bromobenzene 13.2 g (91.9 mmol) of copper (I) bromide were cooled to -5 ° C in 80 ml of dry?,? -dimethylformamide. Under nitrogen atmosphere, 14.7 g (76.7 mmol) of trimethyl (pentafluoroethyl) silane was added. 4.45 g (76.7 mmol) of potassium fluoride (spray-drying) were added in fractions over the course of 30 minutes at a rate such that the internal temperature remained below 0 ° C. The mixture was stirred at 0 ° C for 1 hour and then heated to 20 ° C over the course of 12 hours. Then 10 ml of dry 1, 3-dimethyl-2-imidazolidinone and 22 g (73.1 mmol) of 3-fluoro-4-iodobromobenzene were added. The contents were stirred at 75 ° C for 14 hours. Then all the volatile constituents were distilled to dryness, and the distillate was collected in a cold trap cooled with liquid nitrogen. The distillate was heated to 20 ° C and dissolved in 500 ml of diethyl ether. This solution was washed with 4? 100 ml of water and then 2? 100 ml of a saturated aqueous solution of NaCl. The organic phase was then dried, and the solvent was extracted on a Vigreux column. Subsequent distillation of the residue on a Vigreux column gave 16.1 g of product (boiling point: 86-87 ° C (75 mm Hg)) with a purity of 99% by weight.

Stage 2: Synthesis of 3-fluoro-4- (pentafluoroethyl) benzoic acid A solution of 16.0 g (99% by weight; 54.1 mmol) of 3-fluoro-4- (pentafluoroethyl) bromobenzene in 10 ml of tetrahydrofuran was cooled to -10 ° C. Over the course of 30 minutes, 36.8 ml of a 2M solution (73.6 mmol) of isopropylmagnesium chloride were added dropwise. The mixture was stirred at -10 ° C for 2.5 hours and then poured carefully onto excess dry ice. Then 130 ml of water were added, and the mixture was extracted once with 10 ml of diethyl ether. The aqueous phase was acidified with half-concentrated hydrochloric acid and then extracted with 4 * 150 ml of diethyl ether. The combined organic phases were dried and the filtrate was freed from the solvent. The residue was recrystallized from chloroform to give 10.7 g of product with a purity of 98% by weight.

Stage 3: Synthesis of 3-fluoro-2-methyl-4- (pentafluoroethyl) benzoic acid 5.00 g (98% by weight, 19.0 mmol) of 3-fluoro-4- (pentafluoroethyl) benzoic acid in 40 ml of dry tetrahydrofuran were introduced. 4.73 g (40.7 mmol) of 1,2-bis (dimethylamino) ethane were added, and then the mixture was cooled to -40 ° C. Then 16.3 ml of a 2.5 M solution (40.7 mmol) of n-butyl lithium in hexane were added dropwise at a rate such that the temperature was in a range between -33 ° C and -35 ° C. The contents were stirred at a temperature of -35 ° C for 4 hours. Then a solution of 8.25 g (58.1 mmol) of iodomethane in 10 ml of dry tetrahydrofuran was added dropwise., and the mixture was stirred at -35 ° C for 1 hour. Subsequently the contents were heated to room temperature (RT) and stirred at that temperature for 16 hours. For the final treatment, 50 ml of 2 M hydrochloric acid was carefully added, and then the aqueous phase was extracted with diethyl ether. The combined organic phases were dried and freed from the solvents in a rotary evaporator. The residue was stirred in n-heptane and then filtered. This produced 2.33 g of residue as a clean product. The filtrate was freed from the solvent, and the residue was stirred again in n-heptane. The filtration produced 590 mg of residue, which was identified as a product with a purity of 70% by weight.

Stage 4: Synthesis of methyl 3-fluoro-2-methyl-4- (pentafluoroethyl) benzoate 2.33 g (8.56 mmol) of 3-fluoro-2-methyl-4- (pentafluoroethyl) benzoic acid were introduced into 30 ml of methanol and mixed with 2 ml of concentrated sulfuric acid. The mixture was subsequently heated to reflux temperature until a HPLC check indicated complete conversion. The contents were freed from the solvent in a rotary evaporator, and the residue was taken up in water. The mixture was extracted twice with ethyl acetate, and the combined organic phases were washed once with a saturated aqueous solution of sodium hydrogencarbonate. The organic phase was dried and freed from the solvent. The residue obtained was 2.1 g of clean product.

Stage 5: Synthesis of methyl 2-methyl-3- (methylthio) -4- (pentafluoroethyl) benzoate 2.1 g (7.34 mmol) of methyl 3-fluoro-2-methyl-4- (pentafluoroethyl) benzoate were introduced into 20 ml of DMF and then mixed with 758 mg (95% by weight; mmol) of sodium thiomethoxide. The mixture was stirred at RT for 2 hours and then freed from the solvent. The residue was taken up in ethyl acetate and water, the aqueous phase was extracted twice with ethyl acetate and finally, the combined organic phases were dried and freed from the solvent. The residue was purified by chromatography to give 1.28 g of clean product.

Step 6: Synthesis of 2-methyl-3- (methylthio) -4- (pentafluoroethyl) benzoic acid (No. 6-145) 530 mg (1.69 mmol) of methyl 2-methyl-3- (methylthio) -4- (pentafluoroethyl) benzoate in 10 ml of methanol were introduced and mixed with 0.5 ml of an aqueous solution of sodium hydroxide with a force of 20%. The contents were stirred at RT until a reaction check by thin layer chromatography indicated complete conversion. The mixture was freed from the solvent, and the residue was taken up in a little water. The mixture was acidified with 1 M hydrochloric acid, then stirred for 5 minutes and finally filtered.

The residue obtained was 470 mg of clean product.

Step 7: Synthesis of 4-oxo-bicyclo [3.2.1] oct-2-en-2-yl 2-methyl-3-methylthio-4- (pentafluoroethyl) benzoate 235 mg (0.783 mmol) of 2-methyl-3- (methylthio) -4- (pentafluoroethyl) benzoic acid were introduced into 20 ml of dry dichloromethane and consecutively mixed with 129 mg (1.02 mmol) of oxalyl chloride and also with two drops of?,? - dimethylformamide. After the gas evolution had ended, the mixture was heated to reflux temperature for another 10 minutes. The contents were then cooled and concentrated in a rotary evaporator. The residue was taken up in 20 ml of dry dichloromethane and mixed with 119 mg (0.861 mmol) of bicyclo [3.2.1] octane-2,4-dione and a catalytic amount of DMAP. Then, 158 mg (1.57 mmol) of triethylamine was added dropwise. The mixture was stirred at RT for 16 hours. For the final treatment, 3 ml of 1 N hydrochloric acid was added. After phase separation, the organic phase was freed from the solvent and finally the residue was purified by chromatography. This gave 280 mg of product with a purity of 90% by weight.

Step 8: Synthesis of 4-oxo-bicyclo [3.2.1] oct-2-en-2-yl 2-methyl-3-methylsulfinyl-4-pentafluoroethylbenzoate 280 mg (90% by weight, 0.599 mmol) of 2-methyl-3-methylthio-4-pentafluoroethylbenzoate of 4-oxo-bicyclo [3.2.1] oct-2-en-2-yl were introduced into 20 ml of dichloromethane and mixed with 134 mg (77% by weight; 0.599 mmol) of meia-chloroperbenzoic acid. The mixture was stirred at RT until control of the reaction by thin layer chromatography indicated complete conversion. For the final treatment, the contents were washed once with an aqueous solution of sodium hydrogensulfite with a strength of 10%, and then twice with a saturated aqueous solution of sodium hydrogencarbonate. Finally, the phase organic was released from the solvent. As a residue, 250 mg of product with a purity of 95% by weight were recovered.

Step 9: Synthesis of 3- (2'-methyl-3-methylsulfinyl-4-pentafluoroethylbenzoyl) b] cyclo [3.2.1] octane-2,4-dione (N ° 1-153) 250 mg (95% by weight, 0.544 mmol) of 4-oxo-bicyclo [3.2.1] oct-2-en-2-yl 2-methyl-3-methylsulfinyl-4-pentafluoroethyl-benzoate were introduced into 15 ml of acetonitrile and successively mixed with 110 mg (1.09 mmol) of triethylamine, with a catalytic amount of potassium cyanide and also with eight drops of trimethylsilyl cyanide. The mixture was stirred at RT for 16 hours. For the final treatment, the contents were concentrated, and the residue was taken up in 15 ml of dichloromethane. To the mixture was added 3 ml of 1 M HCl, and after phase separation, the organic phase was freed from the solvent. Finally, the residue was purified by chromatography to give 86.4 mg of product with a purity of 95% by weight.

The examples listed in the following tables were prepared analogously to the procedures identified above or can be obtained by analogy with the procedures identified above. These compounds are very particularly preferred compounds.

The abbreviations used have the following meanings: Bu = butyl Et = ethyl Me = methyl Pr = propyl i = iso s = secondary t = tertiary Ph = phenyl Table 1: Compounds of the invention with the formula (I) wherein R2 is hydroxyl, A is (CH2) and Z is (CH2) 2, and R3 and R4 are each hydrogen Table 2: Compounds of the invention with the formula (I) wherein R2 is hydroxyl, A is oxygen, Z is (CH2) 2, R3 is methyl and R4 is hydrogen Table 3: Compounds of the invention with the formula (I) wherein R 2 is phenylthio, A is (CH 2), Z is (CH 2) 2, and R 3 and R 4 are each hydrogen Compounds of the invention with the formula (I) wherein R 2 is phenylthio, A is oxygen, Z is (CH 2) 2, R 3 is methyl, and R 4 is hydrogen Table 5: Compounds of the invention with the formula (I) wherein R 2 is phenylthio, A is oxygen, Z is (CH 2) 2, R 3 is hydrogen, and R 4 is methyl Table 6: Compounds of the invention with the formula (II) B. Formulation examples 1. Dust A powder is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as an inert substance and grinding the mixture in a hammer mill. 2. Dispersible powders A wettable powder easily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight. of sodium oleoylmethyltaurinate as a wetting and dispersing agent, and milling the mixture in a pin mill. 3. Dispersible concentrate A dispersion concentrate easily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffin mineral oil (boiling range between for example about 255 and above 277 ° C) and grinding the mixture in a ball mill to a size below 5 μm. 4. Emulsifiable concentrate An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohexanone as the solvent and 10 parts by weight of the oxethylated nonylphenol as the emulsifier. 5. Granules dispersible in water The dispersible granules in water are obtained by mixing 75 parts by weight of a compound with the formula (I), 10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulphate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, milling the mixture in a barbed mill and granulating the powder in a fluidized bed by spraying with water as granulation liquid.

Water-dispersible granules are also obtained by homogenising and grinding in a colloid mill beforehand. 25 parts by weight of a compound of the formula (I), 5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-d-sulfonate, 2 parts by weight of sodium oleoylmethyltaurinate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water, subsequently grinding the mixture in a grain mill and pulverizing and drying the resulting suspension in a spray tower by means of a single fluid nozzle.

C. Biological examples 1. Herbicide action against weeds prior to emergence Seeds or parts of the rhizome of mono and dicotyledonous weeds are planted in pots of 9 to 13 cm in diameter, in sandy clay soil, and covered with soil. The herbicides, formulated as emulsifiable concentrates or powders, are applied to the surface of the earth that it covers in the form of dispersions or aqueous suspensions or emulsions, at a water use rate of 300 to 800 l / ha (converted). The pots are kept in a greenhouse under optimum conditions for the subsequent cultivation of the plants. After 3 to 4 weeks under optimal greenhouse growth conditions, the test plants are analyzed with respect to the effect of the compounds according to the invention in comparison with the compounds described in the prior art. As the results of the comparative tables show, the compounds selected according to the invention have a better herbicidal activity against a broad spectrum of monocotyledonous and economically important dicotyledonous weeds than the compounds described in the prior art.

The meanings of the abbreviations used in the comparative tables below are as follows: ALO AND Alopecurus myosuroides AMARE Amaranthus retroflexus AVEFA Avena fatua ECHCG Echinochloa crus galli MATIN Matricaria odorless PHBPU Pharbitis purpureum SETVI Setaria viridis VIOTR Viola tricolor Table 1: Pre-emergence Comparative table 2: Pre-emergence Comparative table 3: Pre-emergence Comparative table 4: Pre-emergence Table 5: Pre-emergence 2. Herbicide action after emergence against weeds Seeds of monocotyledonous and dicotyledonous weeds are planted in cardboard pots on sandy clay soil, covered with soil and grown under greenhouse conditions under good growing conditions. Two to three weeks after sowing, the test plants are treated in the three-leaf stage. The compounds according to the invention, formulated as wettable powders or emulsifiable concentrates, are sprayed on the surface of the green parts of the plants, at a water use rate of 600 to 800 l / ha (converted). After the test plants have been maintained for 3 to 4 weeks under optimal greenhouse growth conditions, the action of the compounds according to the invention is compared with the compounds described in the prior art. As the results of the comparative tables show, the compounds selected according to the invention have a better herbicidal activity against a broad spectrum of monocotyledonous and dicotyledonous weeds. economically important than the compounds described in the prior art.

Comparative table 6: Post-emergence Comparative table 7: Post-emergence Comparative table 8: Post-emergence Comparative table 9: Post-emergency Comparative table 10: Post-emergence Table of contents 11: Post-emer encia

Claims (15)

1. A (4-haloalkyl-3-thiobenzoyl) cyclohexanedione with the formula (I) or a salt characterized because X is (C1-C4) alkyl, Y is haloalkyl (C1-C4) except trifluoromethyl, A and Z are independently from each other oxygen, -S (0) m-, -N (R5) -, carbonyl or alkylene (C1-C4) which is interrupted by q units of the group consisting of oxygen, -S (0) m -, -N (R5) - and carbonyl, and which is substituted with radicals R6, R1 is (C1-C4) alkyl, R2 is hydroxyl, SR7, NR8R9, R3 and R4 are independently from each other hydrogen or (C1-C4) alkyl, R5 is hydrogen, (C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4) alkylcarbonyl, (C1-C4) alkoxycarbonyl, phenylcarbonyl or phenoxycarbonyl, the phenyl ring being in the last two mentioned radicals substituted with up to halogen atoms and with up to p radicals from the group consisting of nitro, cyano, (C 1 -C 4) alkyl, haloalkyl (C 4 C 4), alkoxy (C 1 -C 4) and haloalkoxy (C 4 -C 4), R6 is halogen, (C4) alkyl, (C1-C4) haloalkyl, (C1-C4) alkoxy, (C-C4) haloalkoxy or (Ci-C4) alkoxy (C1-C4) alkyl, R7 is (C1-C4) alkyl or is phenyl which is substituted with p halogen atoms or with p radicals from the group consisting of nitro, cyano, (C1-C4) alkyl, haloalkyl (C1-C4), alkoxy (C4) and haloalkoxy (CrC4), R8 is hydrogen, (C1-C4) alkyl or (Ci-C4) alkoxy, R9 is hydrogen or (C1-C4) alkyl, or R8 and R9, with the nitrogen atom to which they are attached, form a 5 or 6 membered saturated, partially saturated or completely unsaturated ring containing m additional heteroatoms from the group consisting of oxygen, sulfur and nitrogen, and which is substituted with s halogen atoms and with up to p radicals from the group consisting of cyano, alkyl (Ci-C4), haloalkyl (C1-C4), alkoxy (C1-C4) and haloalkoxy (C1-C4), m and n are independently of each other 0, 1 or 2, p is 0, 1, 2, 3, 4 or 5, q is 0 or 1, and s is O, 1, 2, 3, 4, 5, 6, 7 or 8.

2. The (4-haloalkyl-3-thiobenzoyl) cyclohexanedione with the formula (I) according to claim 1, characterized in that X is alkyl (CrC4), Y is haloalkyl (C1-C4) except trifluoromethyl, A and Z are independently oxygen or alkylene (C1-C4), R1 is (C1-C4) alkyl, R2 is hydroxyl, and R3 and R4 are independently hydrogen or alkyl (d-C4).

3. The (4-haloalkyl-3-t-benzoyl) cyclohexanedione with the formula (I) according to claim 1, characterized in that X is (C1-C4) alkyl, And it is trichloromethyl, difluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, pentafluoroethyl or heptafluoroisopropyl, A and Z are each alkylene (C1-C4), R1 is alkyl (C ^), R2 is hydroxyl, and R3 and R4 are independently hydrogen or (C1-C4) alkyl.

4. The (4-haloalkyl-3-thiobenzoyl) cyclohexanedione according to any of claims 1 to 3, characterized in that X is methyl, And it is chlorodifluoromethyl, difluoromethyl or pentafluoroethyl, A and Z are each independently CH2 or CH2CH2, R1 is methyl, R2 is hydroxyl, R3 and R4 are each hydrogen, and n is 1 or 2.

5. The (4-haloalkyl-3-thiobenzoyl) cyclohexanedione in accordance with any of claims 1 to 4, characterized in that X is methyl, And it's pentafluoroethyl, A and Z are each independently CH2 or CH2CH2, R1 is methyl, R2 is hydroxyl, R3 and R4 are each hydrogen, and n is 1 or 2.

6. A herbicidal composition, characterized in that it comprises an effective herbicidal amount of at least one compound of formula (I) as claimed in any of claims 1 to 5.

7. The herbicidal composition according to claim 6, characterized in that it is in a mixture with auxiliary formulation agents.

8. The herbicidal composition according to claim 6 or 7, characterized in that it comprises at least one additional compound with pesticidal activity from the group consisting of insecticides, acaricides, herbicides, fungicides, selective protectants and growth regulators.

9. The herbicidal composition according to claim 8, characterized in that it comprises a selective protector.

10. The herbicidal composition according to claim 8 or 9, characterized in that it comprises an additional herbicide.

11. A method for controlling unwanted plants, characterized in that it comprises the step of applying an effective amount of at least one compound with the formula (I) according to any of claims 1 to 5 or of a herbicidal composition in accordance with any of the claims 6 to 10 to the plants or to the location of the growth of unwanted plants.

12. The use of a compound with the formula (I) as claimed in any of claims 1 to 5 or of a herbicidal composition as claimed in any of claims 6 to 10, for the control of unwanted plants .

13. The use according to claim 12, characterized in that the compound with the formula (I) is used for the control of unwanted plants in crops of useful plants.

14. The use according to claim 13, characterized in that the useful plants are transgenic useful plants.

15. A benzoic acid with the formula (II) characterized in that X, Y, R1 and n are as defined in any of claims 1 to 5.